Metal-azo and metal-azomethine dyes, having a single dye ligand complexed to a metal, are known in the art (see, for example, Drew, H. D. K.; Fairbairn, R. E. J. Chem. Soc. 1939, 823-35; Beech, W. F.; Drew, H. D. K. J. Chem. Soc. 1940, 608-12; Steiner, E.; Mayer, C.; Schetty, G. Helv. Chem. Acta 1976, 59, 364-76; U.S. Pat. Nos. 4,012,369; 4,123,429; and 4,265,811). These 1:1 complexes are predominantly used in two applications; color photography (U.S. Pat. Nos. 3,453,107; 3,551,406; 3,544,545; 3,563,739; 3,597,200; 3,705,184; 3,752,836; 3,970,616; 4,150,018; and 4,562,139), and the dyeing of textiles (U.S. Pat. Nos. 3,878,158; 4,045,423; 4,218,367; and 4,617,382; and European Pat. No. 144776). The 1:1 complexes have a central metal ion coordinated to a dye and additional ligands (e.g., water, pyridine, ammonia, or ethanolamine).
Metal complexes containing a polymerizable functionality are also known. For example metal-vinylpyridine complexes are known which are capable of polymerization (U.S. Pat. No. 3,287,455 and Agnew, N. H.; Collin, R. J.; Larkworthy, L. F. J. Chem. Soc. Dalton Trans. 1974, 272-7). Generally, the extinction coefficients of visible wavelength transitions in polymerizable metal complexes of the prior art are less than 1000M.sup.-1 cm.sup.-1 which make them, in general, unsuitable as dyes or colorants.
Many transition metal complexes with vinylpyridine as a ligand are unstable. Some of these complexes are quite labile in solution, exhibiting the following equilibrium: EQU M(ligand).sub.x (vinylpyridine).sub.n .revreaction.M(ligand).sub.x (vinylpyridine).sub.n-1 +vinylpyridine
Additionally, transition metals, such as copper(II) and ruthenium(III), may initiate the polymerization of vinylpyridine (e.g., Tazuke, S.; Okamura, S. J. Polym. Sci.: Part A-1 1966, 4, 141-57; and Norton, K. A., Jr.; Hurst, J. K. J. Amer. Chem. Soc. 1978, 100, 7237-42), although some stable complexes of copper(II) and vinylpyridine have been reported (Laing, M.; Horsfield, E. J. Chem. Soc., Chem. Commun. 1968, 735).
Vinyl groups on ligands may undergo cyclometallation or coordinate to the metal, thereby rendering them non-polymerizable (Newkome, G. R.; Theriot, K. J.; Cheskin, B. K.; Evans, D. W.; Baker, G. R. Organometallics 1990, 9, 1375-9; and Long, C.; Kelly, J. M. J. Organometal. Chem. 1982, 231, C9).
Metal-containing polymerizable complexes which absorb light more strongly than the vinylpyridine complexes are also known in the art (Sheats, J. E.; Carraher, C. E., Jr.; Pittman, C. U., Jr. in Metal-containing Polymeric Systems; Plenum Press: New York, 1985). The most studied systems are vinylcyclopentadienyl complexes of low valent metals. These metal-containing monomers are usually very electron rich, and the polymeric material derived from these monomers are often easily oxidized.
It has been shown that (4-vinyl-4'-methyl-bipyridyl)Re(CO).sub.3 Cl undergoes chemical changes, under some conditions, when exposed to filtered sunlight (O'Toole, T. R.; Sullivan, B. P.; Meyer, T. J. J. Am. Chem. Soc. 1989, 111, 5699-706). The chemical and photochemical reactivities of these molecules suggest they would not be useful polymerizable dyes.
Advantages of metal-containing polymeric dyes have been taught in the art (Marechal, E. Progress in Organic Coatings 1982, 10, 251-87; and Asquith, R. S.; Blair, H. S.; Crangle, A. A.; Riordan, E. J. Soc. Dyers Colour. 1973, 93, 115). Most of these polymers involve colorants other than azo, hydrazone, or azomethine dyes and are derived from monomers not containing free-radically polymerizable groups.
U.S. Pat. No. 4,218,367 describes the preparation and use of 1:1 chromium metal-azo dyes containing reactive groups. In claim 5 of that patent, 1:1 complexes, where the reactive group is a vinyl sulfone directly bound to the azo ligand, are claimed. There are no examples given wherein a vinyl sulfone group was actually present. Dyes of that patent react with preformed polymers such as cellulose. There are no examples in that patent of forming polymers using dyes containing a vinyl sulfone group.
Poly(vinylpyridine) and copolymers containing vinylpyridine are used in mordanting receiving layers in photographic films (for example, U.S. Pat. No. 4,282,305). Unmetallized dyes diffuse to the receiving layer and form a metal complex which is presumably attached to poly(vinylpyridine). The ratio of dye to vinylpyridine is not controlled.
What the foregoing art does not disclose or teach is that metal-dye complexes having ligands with polymerizable groups may be conveniently made and polymerized to provide stable mordanted dyes.